Li＋交换的几种分子筛的氮氩分离性能

采用水溶液离子交换法制备了高Li＋交换度的4A、13X和LSX分子筛,并在25 ℃下测定了它们的静态吸附等温线和动态穿透曲线.研究发现,高Li＋离子交换度的4A、13X和LSX分子筛都具有较大的氮吸附容量和较高的氮氩分离选择性,说明高Li＋离子交换度的4A、13X和LSX分子筛是较好的氮氩分离吸附剂.从动态穿透曲线结果来看,所研究的三种分子筛都有一个最优的吸附分离压力,在本文研究的压力范围内,这个最优压力在0.6 MPa附近.对比高锂交换度的三种分子筛,以高锂交换度的LSX分子筛的氮氩吸附分离性能最好.     

Ca2+交换的几种分子筛的氮氩分离性能

采用水溶液离子交换法制备了Ca2+交换的4A,13X和LSX分子筛,并在25 ℃下测定了它们的静态吸附等温线和动态穿透曲线.研究发现, Ca2+交换的4A,13X和LSX分子筛对氮的吸附性能都明显优于其相应的钠型分子筛,而它们对氩的吸附量变化不大,说明Ca2+交换的这三种分子筛是较好的氮氩分离吸附剂.从动态吸附的结果来看,所研究的各种分子筛都有一个最优的吸附分离压力,在本论文研究的压力范围内,这个最优压力在0.6 MPa附近.由穿透曲线可推算出混合气体的吸附量,通过氮和氩在混合气体中的吸附量和相应纯气体吸附量的对比可以得出,对于氮氩吸附选择性较高的分子筛,氮的存在对氩的吸附量有较大的影响.     

Ca2＋交换的几种分子筛的氮氩分离性能

采用水溶液离子交换法制备了Ca2＋交换的4A、13X和LSX分子筛，并在25 ℃下测定了它们的静态吸附等温线和动态穿透曲线.研究发现， Ca2＋交换的4A、13X和LSX分子筛对氮的吸附性能都明显优于其相应的钠型分子筛，而它们对氩的吸附量变化不大，说明Ca2＋交换的这三种分子筛是较好的氮氩分离吸附剂.从动态吸附的结果来看，所研究的各种分子筛都有一个最优的吸附分离压力，在本论文研究的压力范围内，这个最优压力在0.6 MPa附近.由穿透曲线可推算出混合气体的吸附量，通过氮和氩在混合气体中的吸附量和相应纯气体吸附量的对比可以得出，对于氮氩吸附选择性较高的分子筛，氮的存在对氩的吸附量有较大的影响.     

N2和Ar在改性的NaA分子筛上的吸附分离

采用水溶液离子交换法分别制备了不同Li^ 和Ca^2^ 交换度的A型分子筛,并在25℃下测定了各分子筛吸附剂的氮和氩的吸附等温线及穿透曲线．研究发现,锂交换和钙交换的两种分子筛的氮吸附量和氮氩分离选择性都随分子筛中阳离子交换度的增加而增大;在阳离子交换度较高时,锂离子和钙离子交换的A型分子筛的氮氩分离能力均优于NaA分子筛．穿透曲线的结果显示,所研究的各种吸附剂都存在一个最优的吸附分离压力,大约在0．6MPa．在0．6MPaT,接近100％阳离子交换度的CaNaA分子筛的动态氮氩分离性能优于相同交换度的LiNaA分子筛。     

低温变压分子筛动态分离CH_4/CO_2实验研究

在低温变压条件下测量了5A和13X沸石分子筛对CH_4/CO_2混合气体的分离能力。实验研究了CH_4/CO_2气体流量、吸附压力、填料高度和吸附温度对穿透曲线和分离能力的影响。研究结果表明,增大气体流量、增加吸附压力会降低分离效果,减小混合气体的分离系数;降低吸附温度、增加填料高度有利于CH_4/CO_2分离,提高混合气体的分离系数;在相同实验条件下,13X沸石分子筛对CH_4/CO_2混合气体吸附分离能力高于5A分子筛。     

几种二价阳离子的交换对13X分子筛氮氩分离性能的影响

采用水溶液离子交换法分别制备了不同二价阳离子(Mg²⁺、Zn²⁺和Ca²⁺)交换的13X型分子筛，并在25 ℃下测定了各分子筛吸附剂的氮和氩的吸附等温线。研究发现，13X分子筛经Mg²⁺和Zn²⁺交换后，吸附剂的吸氮能力及氮氩分离能力降低；13X分子筛经Ca²⁺交换后，吸附剂的吸氮能力及氮氩分离能力随分子筛中钙离子交换度的增加而增大。对常压氮氩分离性能较好的CaNaX系列分子     

氮、氩在5分子筛上的低温吸附分离

测定了不同温度下氮、氩在5分子筛上的吸附等温线,其中三参数的Langmuir-Freundlich方程和Toth方程在不同温度下都能获得较好的拟合结果;计算了不同温度下氮、氩在5分子筛上吸附的亨利常数,获得了氮、氩选择性和温度的关系。测定了125K温度下氮、氩混合气体在5分子筛吸附柱上的穿透曲线。结果表明:最先流出的5L气体中含有约70%的氩,通过收集5L气体即可实现混合气体中氩的初步分离。     

氮、氩在5A^。分子筛上的低温吸附分离

测定了不同温度下氮、氩在5分子筛上的吸附等温线,其中三参数的Langmuir-Freundlich方程和Toth方程在不同温度下都能获得较好的拟合结果;计算了不同温度下氮、氩在5分子筛上吸附的亨利常数,获得了氮、氩选择性和温度的关系.测定了125K温度下氮、氩混合气体在5分子筛吸附柱上的穿透曲线.结果表明:最先流出的5L气体中含有约70%的氩,通过收集5L气体即可实现混合气体中氩的初步分离.     

4A沸石分子筛对氮、氧、氩的吸附分离特性

用PSA法的动态吸附装置,宏观地考察了在压力下、于NaA上氮、氧、氩单一组份的和在二元体系中的吸附分离特性,企图从这一角度解释4A沸石分子筛在PSA过程中能制取富氮气体的原因。     

Cu(Ⅰ)NH4Y吸附剂的制备及其乙烯/乙烷吸附分离性能

本研究采用液相离子交换法,用不同浓度的CuCl2对NH₄Y分子筛进行离子交换制得系列CuNH₄Y-x分子筛吸附剂,并通过固定床吸附穿透实验及一系列表征手段探究了Cu的价态和负载量对乙烯/乙烷吸附分离性能的影响。吸附穿透实验结果表明,Cu(Ⅰ)NH₄Y0.10的乙烯吸附量明显高于Cu(Ⅱ)NH₄Y0.10,且Cu(Ⅰ)NH₄Y系列吸附剂的乙烯吸附量随着Cu负载量的增加呈现先增加后减小的趋势。H₂-TPR和HRTEM表明,当Cu的负载量较低时,高度分散落位于Y分子筛超笼中的Cu(Ⅰ)物种是乙烯有效吸附位点。然而,当Cu的负载量较高时,部分Cu物种发生团聚,造成对乙烯吸附能力的减弱。DFT密度泛函理论计算表明相比于Cu(Ⅱ)NH₄Y吸附剂,乙烯更容易吸附在Cu(Ⅰ)NH₄Y吸附剂上。该研究结果可为乙烯分离用高效Cu离子改性分子筛吸附剂的开发提供重要理论依据与指导。     

Separation of CO_2–N_2 using zeolite NaKA with high selectivity

The adsorption method based on solid adsorbents is one of feasible ways to capture and store CO_2. Using the ion exchange method, different zeolites Na KA varying in K+content were produced. The adsorption isotherms and kinetic uptakes were measured. The experimental results show that the optimal NaKA could adsorb significant quantities of CO_2 and little N_2. On the zeolite Na KA with 14.7 at.% K+, the adsorption capacity for pure CO_2 is over 3.10 mmol g~(-1) and the CO_2–N_2 selectivity is about 149 at ambient pressure and temperature. The kinetic CO_2–N_2 selectivity could also achieved 200 within 3 min according to the uptake data. To demonstrate the separation effectiveness, breakthrough curves of pure components and binary mixtures were investigated experimentally and theoretically in a fixed bed. It is found that the breakthrough points of CO_2 and N_2 are almost at the same time under the atmospheric pressure at 348 K with the raw gas composition CO_2/N_2(20:80, v/v). If the pressure has been increased higher than 0.1 MPa, CO_2 would break through the bed much slower than N_2. Therefore, the pressure may become the limiting factor for the separation performance of zeolites NaKA.     

Theoretical study of the adsorption of ethylene on alkali‐exchanged zeolites

The structures of alkali‐exchanged faujasite (X–FAU, X = Li⁺ or Na⁺ ion) and ZSM‐5 (Li–ZSM‐5) zeolites and their interactions with ethylene have been investigated by means of quantum cluster and embedded cluster approaches at the B3LYP/6‐31G(d, p) level of theory. Inclusion of the Madelung potential from the zeolite framework has a significant effect on the structure and interaction energies of the adsorption complexes and leads to differentiation of different types of zeolites (ZSM‐5 and FAU) that cannot be drawn from a typical quantum cluster model, H₃SiO(X)Al(OH)₂OSiH₃. The Li–ZSM‐5 zeolite is predicted to have a higher Lewis acidity and thus higher ethylene adsorption energy than the Li–FAU zeolites (16.4 vs. 14.4 kcal/mol), in good agreement with the known acidity trend of these two zeolites. On the other hand, the cluster models give virtually the same adsorption energies for both zeolite complexes (8.9 vs. 9.1 kcal/mol). For the larger cation‐exchanged Na–FAU complex, the adsorption energy (11.6 kcal/mol) is predicted to be lower than that of Li–FAU zeolites, which compares well with the experimental estimate of about 9.6 kcal/mol for ethylene adsorption on a less acidic Na–X zeolite. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 333–340, 2003     

金属离子交换分子筛的NO吸附性能

在固定床流动吸附装置上利用吸附一脱附法测定了各种金属离子交换分子筛上NO吸附性能．结果表明，在ZSM－5上NO的可逆吸附量（qrev）与不可逆吸附量（qiir）随交换金属离子的不同而不同．单位交换金属离子的NO可逆吸附量（qrev）与不可逆吸附量（qiir）随分子筛铝含量的减少而增加．qrev与qiir在ZSM－5分子筛上不随交换度变化，而在丝光沸石上却随交换度的变化而改变．     

Study on the adsorption of 1,5-, 1,6- and 2,6-dimethylnaphthalene on a series of alkaline and alkaline earth ion-exchanged faujasite zeolites

Adsorption of the equilibrium mixture of 1,5-, 1,6- and 2,6-dimethylnaphthalene (DMN) was investigated on a series of alkaline and alkaline earth ion-exchanged faujasite zeolites using pulse test and breakthrough techniques. It was found that the adsorption of the DMNs would proceed through a complex mechanism governing by at least molecular diffusion, acid-base interaction, preferential interaction with cation and molecular displacement. All ion-exchanged faujasite zeolites only provided rejective systems for 2,6-DMN and some of them were potential adsorbents for the 2,6-DMN purification.     

镧改性的CuHY分子筛中铜离子的分布及其对吸附脱硫性能的影响

在氮气气氛下采用等体积浸渍法制备了载Cu的HY和LaHY分子筛.用x射线衍射(XRD)、N2吸附、氨程序升温脱附和X射线光电子能谱对分子筛进行了表征.通过多晶XRD确定了Cu2+离子在Y型分子筛笼内的结构与分布,并测定了分子筛在含二苯并噻吩(DBT)的模拟柴油中的吸附脱硫性能.结果表明,前驱体CuCl2中的大部分Cu物种与HY和LaHY分子筛进行了离子交换.对于La3+改性的CuHY分子筛(CuLaHY),进入分子筛超笼中的Cu2+离子与骨架氧和水分子配位,牢固地定位于Y型分子筛超笼的SⅡ及SⅢ位;对于CuHY分子筛,超笼中的Cu2+离子只接近于SⅡ及SⅢ位.极少部分CuCl分子高度分散在分子筛笼内,没有定位.处于超笼中SⅡ及SⅢ位的Cu2+离子对模拟柴油中的DBT分子具有吸附作用,是吸附脱硫的活性中心.CuLaHY分子筛的吸附脱硫性能优于CuHY分子筛.当模拟柴油中含有萘时,萘与DBT分子会产生竞争吸附.     

Deep desulfurization of FCC gasoline by selective adsorption over nanosized zeolite-based adsorbents

Deep desulfurization of FCC gasoline by selective absorption was performed on various ion-exchanged nanosized Y zeolites. It was found that the metal ion as well as calcination conditions have significant influence on the absorption performance. The highest S absorption capacity was obtained on a HCuCeY sample calcined in N₂ atmosphere.     

Adsorption of Nitrogen, Oxygen and Argon on Na-CeX Zeolites

Commercial type X zeolites (Linde 13X) are nitrogen selective. Oxygen is the less abundant component in air; hence oxygen selective sorbents are desired for air separation. Mixed Na-Ce type X zeolites containing different ratios of Ce³⁺/Na⁺ ions are prepared by partial ion exchange of commercial X zeolite. The adsorption isotherms of nitrogen, oxygen and argon are measured and the pure-component selectivity ratios are compared and analyzed against commercial zeolites (13X) for air separation. Oxygen selectivity over nitrogen (1.5) and argon (4.0) are seen for mixed Na-Ce type X zeolite (Si/Al = 1.25; Ce³⁺/Na⁺ < 4.0) from Henry's constant determined from low pressure adsorption measurements. The oxygen and nitrogen isotherms cross over for mixed Na-Ce type X zeolite (Si/Al = 1.25; Ce³⁺/Na⁺ < 4.0), and the pressure at which cross they over increases as Ce³⁺/Na⁺ approaches 1. The oxygen selectivity as claimed in the patent by N.V. Choudary, R.V. Jasra, and S.G.T. Bhat (US Patent no. 6,087,289, 2000) is seen only at very low pressures in the volumetric adsorption measurement and the hydrogen treatment of the Ce-exchanged samples have no effect on the adsorption characteristics.     

Adsorptive removal of halo-olefinic impurities from 1,1,1,3,3-pentafluoropropane over ion-exchanged Y zeolites

Various metal cations exchanged Y zeolites were prepared via the exchange of NaY zeolite with aqueous solutions containing K⁺, Ca²⁺, Cu²⁺, La³⁺ and Ce³⁺ cations, respectively. The influence of the extra-framework cations nature of these ion-exchanged Y zeolites on their adsorption performance for a low content of halo-olefinic impurities, mainly including 1-chloro-3,3,3-trifluoro-1-propene (HCFC-1233zd), 1-chloro-1,3,3,3-tetrafluoro-1-propene (HFC-1224zb) and 2-chloro-1,3,3,3-tetrafluoro-1-propene (HFC-1224xe), in the 1,1,1,3,3-pentafluoropropane (HFC-245fa) product after distillation was investigated. HCFC-1233zd impurity can be substantially removed from HFC-245fa product feed via the adsorption over multivalent metal cations and Cu⁺ cation exchanged Y zeolites, which is ascribed to the formation of π-adsorption complexes between HCFC-1233zd and zeolites, rather than over alkaline metal cations exchanged Y zeolites. Among multivalent metal cations exchanged Y zeolites, CeY has the highest adsorption capacity for HCFC-1233zd and best regeneration performance, due to its lowest density of strong Brønsted and weak Lewis acid sites as well as high framework stability during the regeneration. Regardless of the cations introduced in Y zeolite used as an adsorbent, HCFC-1224zb and HCFC-1224xe impurities are not obviously removed from HFC-245fa product feed via the adsorption, maybe due to more halogen atoms linked with the double bond in them comparing with HCFC-1233zd.